Semi-Additive Process for Printed Circuit Boards

ABSTRACT

A circuit board has a dielectric core, a foil top surface, and a thin foil bottom surface with a foil backing of sufficient thickness to absorb heat from a laser drilling operation to prevent the penetration of the thin foil bottom surface during laser drilling. A sequence of steps including a laser drilling step, removing the foil backing step, electroless plating step, patterned resist step, electroplating step, resist strip step, tin plate step, and copper etch step are performed, which provide dot vias of fine linewidth and resolution.

FIELD OF THE INVENTION

The present invention relates to a circuit board and an associatedmethod for fabrication. In particular, the invention is related to acircuit board and method for forming fine pitch vias and associated finepitch traces.

BACKGROUND OF THE INVENTION

Prior art printed circuit boards (PCBs) are formed using conductivemetal interconnects (known as “traces”) formed on a dielectricsubstrate. Conductive apertures are formed on the circuit board tobridge traces on opposite sides of the dielectric substrate, where theconductive apertures which have a larger diameter and may be used formounting components are known as “through holes” and a minimal diameterconductive aperture which is used to interconnect traces on oppositesides is known as a “dot via” (prior to the formation of traces) orsimply “via” (after the traces are formed). Each surface carrying traceconductors is known as a “layer”, and each dielectric substrate havingtraces formed on one surface or on both surfaces form a “sub”, which isa fundamental subassembly of a multi-layer board. By stacking severalsuch subs, each sub comprising a dielectric core having traces andinterconnecting vias interspersed with bare dielectric layers, andlaminating them together under temperature and pressure, a multi-layerprinted circuit may be formed. The dielectric substrate may comprise anepoxy resin embedded in a fiber matrix such as glass fiber woven into acloth.

One difficulty of prior art circuit board fabrication is the formationof deep (high aspect ratio) vias and fine pitch vias. Becauseelectroplating operations consume the metal ions in solution, it isdifficult to form vias with high aspect ratios, as the more distantregions of the via from the metal ion bath have lower concentrations ofmetal ions for deposition than regions of the via which are near to, andreplenished by, the circulating ion bath. Small diameter vias aresimilarly diameter-limited by the aspect ratio of the via, which isgoverned by the thickness of the circuit layer to be formed. Blind vias(which are open on one end only) limit the circulation of metal ions insolution at the closed end of the via.

Another difficulty of fine pitch circuit board fabrication is that dotvia structures are formed in a first step, through holes are formed in aseparate step, and traces are formed in a subsequent step. It is desiredto form dot vias, through hole plating, and traces in a singleelectroplating step. It is also desired to form vias having the aspectratio for a single layer but which are continuous through multiplelayers, thereby forming stacked vias. It is also desired to provide amethod which provides for reduced diameter vias and fine pitch tracesfor use in fabricating fine pitch PCBs.

Objects of the Invention

A first object of the invention is a process for forming a circuit layerhaving dot vias, stacked vias, through holes, and traces, the processutilizing a dielectric having a thin conductive foil layer applied to abottom surface and a comparatively thick backing foil layer applied tothe thin conductive foil, the circuit layer optionally also having a topsurface conductive foil applied opposite the bottom surface, the circuitlayer subsequently having a blind via drill step whereby a laser ablatesthe dielectric to the level of the bottom thin foil layer, the backinglayer removing heat from the bottom foil to prevent penetration ormelting of the thin foil during laser ablation of the dielectric, and anoptional through hole step for drilling holes through all layers of theboard and foil layers, a thick backing foil removal step, electrolessdeposition of copper on thin foil and exposed dielectric surfaces in anelectroless deposition step, a pattern resist step applied to at leastone surface of the circuit layer, an electro plating step depositingcopper on unmasked copper areas, a secondary plate mask step depositinga mask material such as tin on exposed copper areas, a resist stripstep, and a quick etch step to remove the electroless depositionmaterial such as copper which is not coated with the secondary platematerial such as tin, and a quick etch step to remove the secondaryplate mask material such as tin.

A second object of the invention is a circuit board having been made byapplying a thin foil to a bottom surface of a dielectric, applying athick backing foil to the bottom surface tin foil, optionally applying afoil to the top surface of the dielectric opposite the bottom surface,laser drilling or ablating material from the top surface through thedielectric and down to the bottom thin foil without penetration of thebottom thin foil, the penetration of the bottom thin foil prevented bythickness selection of the backing foil as a heat sink, thereafterremoving the backing foil, thereafter electroless plating the circuitboard, thereafter applying patterned resist to at least one surface,thereafter electroplating the circuit board, the electroplatingoperative on exposed copper of the circuit board, thereafter plating theexposed copper with a mask material such as tin, thereafter performing aquick etch of exposed copper to remove copper which has not been platedwith the mask material such as tin, thereafter optionally performing aquick etch to remove any exposed tin.

A third object of the invention is a multilayer circuit board formed by:

forming an inner layer from a dielectric having a thin conductive layeron a top and bottom surface, the conductive layers having acomparatively thick foil applied to each surface, the comparativelythick foil removed from a top surface, holes drilled through the topfoil and dielectric such as by laser to form via apertures, the laserdrilled via apertures prevented from penetrating the top foil by theheat sinking capability of the bottom surface comparatively thick foil,removing the bottom surface comparatively thick foil, electro-lessplating the exposed dielectric surfaces and foil surfaces, applying aresist pattern to the top surface and the bottom surface,electro-plating the exposed copper surfaces not covered by resist untilat least one via aperture is plugged, tin plating the exposed coppersurfaces not covered by resist, stripping the photoresist, quick etchingthe exposed copper surfaces sufficiently to remove copper previouslycovered by photoresist, and optionally etching the tin plating;

adding one or more pairs of outer layers to the inner layer,

-   -   each outer layer formed by laminating the non-foil side of a        dielectric having one surface covered with foil to the inner        layer, thereafter drilling at least one via aperture on at least        one outer layer which is substantially over an inner layer        filled via, thereafter electroless plating the via apertures and        exposed foil surfaces, thereafter applying a pattern mask,        thereafter electro-plating the via apertures and exposed foil        surfaces, thereafter tin plating the exposed copper surfaces,        thereafter stripping the pattern mask, thereafter quick etching        the foil and electroless plating which was under the pattern        mask until the foil and electroless plating is removed,        thereafter optionally stripping the tin, thereby forming a new        inner layer for subsequent outer layers to be applied.

SUMMARY OF THE INVENTION

In a first embodiment of the invention, at least one via is formed on acircuit board, the circuit board having a bottom surface covered with abottom thin copper foil and a comparatively thick layer of removablecopper backing foil placed over the bottom thin copper foil, the circuitboard optionally having a top surface thin copper foil applied to a topsurface opposite the bottom surface, the circuit board thereafter havinglaser drilled blind holes formed from the top surface to the bottom thincopper foil, but not penetrating through the thin copper foil, thecopper backing foil having a sufficient thickness to prevent the heatdeveloped by the laser from ablating the first thin copper foil bycoupling thermal energy to the backing foil and surrounding region ofbacking foil. The backing foil is then removed upon completion ofdrilling the holes or via apertures. The ablated via apertures and anythrough holes have catalytic inner surfaces, such as either by use of acatalytic dielectric laminate, or by application of catalyst to theexposed via aperture surfaces during a desmearing operation. The circuitboard is thereafter exposed to an electroless plating bath of metal ionssuch as copper, which bind to the catalytic particles present in the viaaperture and spread until a continuous deposition is made in the viaaperture surfaces and through hole aperture surfaces, as well as in thecopper foil areas, creating a uniformly conductive surface forsubsequent electro-plating. Patterned resist is next applied, whichprevents depositions from a subsequent electro-plating operation fromforming in areas covered by resist. Using the continuous conductivesurface and exposed regions without resist, the circuit board is used asan electrode in an electro-plating step performed until the electrolesscopper deposition reaches the depth of the photoresist, or a desireddepth typically less than the photoresist thickness. A tin plate stepsubsequently deposits tin over the exposed copper surfaces, which servesas an etching mask for a subsequent copper etch operation, after whichthe photoresist is stripped, leaving tin-masked copper and exposedcopper. A quick etch of exposed copper removes the exposed coppercomprising thin bottom copper foil and the optional top copper foilwhich was in patterned photoresist areas. After removal of the exposedcopper in the quick etch step, which leaves the tin-masked copperunaltered, the tin is optionally etched. The resultant vias areconductively plugged and mechanically smaller than vias produced byprior art processes.

BRIEF DESCRIPTION OF THE DRAWINGS

FIGS. 1A, 1B, 1C, 1D, 1E, 1F, 1G, 1H, 1I, 1J, 1K, 1L, 1M, and 1N showcross section views of processing steps for a standard linewidth processfor forming traces and dot vias for an inner layer of a multi-layerboard or a two layer circuit board.

FIGS. 2A, 2B, 2C, 2D, 2E, 2F, 2G, 2H, 2I, and 2J show cross sectionviews of processing steps for forming traces and dot vias for an innerlayer of a multi-layer board or a two layer circuit board.

FIGS. 3A, 3B, 3C, 3D, 3E, 3F, 3G, and 3H show cross section views ofprocessing steps for a multi-layer fine linewidth process.

FIGS. 4A, 4B, 4C, 4D, 4E, 4F, 4G, and 4H show cross section views of theprocessing steps for forming traces and vias on an inner layer of amulti-layer board or a two layer board using a catalytic laminate.

FIGS. 5A, 5B, and 5C show cross section views of the processing stepsfor a multi-layer board fine linewidth process using a catalyticlaminate.

DETAILED DESCRIPTION OF THE INVENTION

FIG. 1A shows cross section of a dielectric 102 having an optional topsurface foil 104A and bottom surface foil 104B, which are approximately0.3 mil (7.5 u) thick. Dielectric 102 comprises a mixture of reinforcingfibers and epoxy resin. Many different materials may be used for thefibers of pre-preg, including woven glass-fiber cloth, carbon-fiber, orother fibers, and a variety of different materials may be used for theresin, including epoxy resin, polyimide resin, cyanate ester resin, PTFE(Teflon) blend resin, or other resins. Deposition of conductors such ascopper may be performed using two different plating techniques. In afirst electroless plating technique, the dielectric layer is formed bymixing the resin with catalytic particles which attract copper ions. Therate of electroless metallic copper deposition is slower thanelectroplating, but the deposition occurs on all surfaces which haveexposed catalytic particles, as well as on surfaces which have exposedcopper. Electro-plating provides a faster rate of copper depositionbecause it utilizes a sacrificial copper anode having a positive voltageis placed into an electrolyte bath, with the surface to be platedconnected to a negative voltage. The copper migrates as metal ions fromthe anode through the electrolyte to the cathodic surface. In thepresent example, the cathodic surface is the PCB needing copper plating.Electroplating requires that all surfaces have a common potential, whichis typically accomplished using a pre-existent copper foil or apreceding electroless plating step on a dielectric surface havingexposed catalytic particles until continuous electrical conductivityacross the entire board allows for the board to be used as a cathode, asrequired for an anodic copper source. Electroless plating may be in therange 0.06 mil (1.5 u) to 0.12 mil (3 u) to provide sufficient surfaceconductivity for electroplating.

While the description is drawn to the formation of copper vias andtraces using catalysts for electroless copper formation, it isunderstood that the scope of the invention may be extended to othermetals suitable for electroless plating and electro-plating. Forelectroless deposition of copper (Cu), elemental palladium (Pd) ispreferred as the catalyst, although selected periodic table transitionmetal elements, such as group 9 to 11 platinum (Pt), rhodium (Rh),iridium (Ir), nickel (Ni), gold (Au), silver (Ag), cobalt (Co), orcopper (Cu), or other compounds of these, including other metals such asiron (Fe), manganese (Mn), chromium (Cr), molybdenum (Mo), tungsten (W),titanium (Ti), tin (Sn), or mixtures or salts of the above, any of whichmay be used as catalytic particles. The present candidate list isintended to be exemplar rather than comprehensive, it is known in theart that other catalysts for attracting copper ions may also be used. Inone example of the invention suitable for use in a catalytic laminate,the catalytic particles are homogeneous catalytic particles. In anotherexample of the invention forming a catalytic laminate, the catalyticparticles are inorganic particles or high temperature resistant plasticparticles which are coated with a few angstrom thickness of catalyticmetal, thereby forming heterogeneous catalytic particles having a thincatalytic outer surface encapsulating a non-catalytic inner particle.This formulation may be desirable for larger catalytic particles, suchas those on the order of 25 u in longest dimension. The heterogeneouscatalytic particle of this formulation can comprise an inorganic,organic, or inert filler such as silicon dioxide (SiO₂), an inorganicclay such as Kaolin, or a high temperature plastic filler coated on thesurface with a catalyst such as palladium adsorbed onto the surface ofthe filler, such as by vapor deposition or chemical deposition. Only afew atomic layers of catalyst are required for the catalytic particle tohave desirable properties conducive to electroless plating.

In one example of forming heterogeneous catalytic particles, a bath offillers (organic or inorganic) is sorted by size to include particlesless than 25 u in size, these sorted inorganic particles are mixed intoan aqueous bath in a tank, agitated, and then a palladium salt such asPdCl (or any other catalyst such as a salt of silver of other catalyst)is introduced with an acid such as HCl, and with a reducing agent suchas hydrazine hydrate, the mixture thereby reducing metallic Pd whichcoats the inorganic particles provide a few angstroms of thickness of Pdcoated on the filler, thereby creating a heterogeneous catalyticparticle which has the catalytic property of a homogeneous Pd particlewith a greatly reduced volume requirement of Pd compared to usinghomogeneous Pd metallic particles. For extremely small catalyticparticles on the order of a few nm, however, homogeneous catalyticparticles (such as pure Pd) may be preferred.

Example inorganic fillers include clay minerals such as hydrous aluminumphyllosilicates, which may contain variable amounts of iron, magnesium,alkali metals, alkaline earths, and other cations. This family ofexample inorganic fillers includes silicon dioxide, aluminum silicate,kaolinite (Al₂Si₂O₅(OH)₄), polysilicate, or other clay minerals whichbelong to the kaolin or china clay family. Example organic fillersinclude PTFE (Teflon) and other polymers with high temperatureresistance.

Examples of palladium salts are: BrPd, CL₂Pd, Pd(CN)₂, I₂Pd,Pd(NO₃)₂*2H₂O, Pd(NO₃)₂, PdSO₄, Pd(NH₃)4Br₂, Pd(NH₃)4Cl₂H₂O. Thecatalytic powder of the present invention may also contain a mixture ofheterogeneous catalytic particles (for example, catalytic materialscoated over inorganic filler particles), homogeneous catalytic particles(such as elemental palladium), as well as non-catalytic particles(selected from the family of inorganic fillers).

Among the catalysts, palladium is a preferred catalyst because ofcomparative economy, availability, and mechanical properties, but othercatalysts may be used.

The resin may be a polyimide resin, a blend of epoxy and cyanide ester(which provides curing at elevated temperatures), or any other suitableresin formulation with selectable viscosity during coating andthermosetting properties after cooling. Fire retardants may be added,for example to comply with a flammability standard, or to be compatiblewith one of the standard FR series of pre-preg such as FR-4 or FR-10. Anadditional requirement for high speed electrical circuits is dielectricconstant ε (permittivity), which is often approximately 4 and governsthe characteristic impedance of a transmission line formed on thedielectric, and loss tangent δ, which is measure of frequency-dependentenergy absorption over a distance, whereby the loss tangent is a measureof how the dielectric interacts with high frequency electric fields toundesirably reduce signal amplitude by a calculable amount of dB per cmof transmission line length. The resin is blended with catalyticparticles which have been sorted for size. In one example formulation,the catalytic particles include at least one of: homogeneous catalyticparticles (metallic palladium), or heterogeneous catalytic particles(palladium coated over an inorganic particle or high temperatureplastic), and for either formulation, the catalytic particles preferablyhaving a maximum extent of less than 25 u and with 50% of the particlesby count sized between 12 u and 25 u, or the range 1-25 u, or smallerthan 25 u. These are example catalytic particle size embodiments notintended to limit the scope of the invention. In one example embodiment,the catalytic particles (either homogeneous or heterogeneous) are in thesize range 1 u-25 u. In another example of the invention, homogeneouscatalytic particles are formed by grinding metallic palladium intoparticles and passing the resultant particles through a sieve with amesh having 25 u rectangular openings such that all catalytic particlessmaller than 25 u are selected, and the grinding operation determinesthe aspect ratio of the particles in the smallest dimension direction.Aspect ratios less than 2:1 are preferable, but not limited to thatrange for the present example embodiment, and the catalytic particlesmay be heterogeneous or homogeneous catalytic particles. In anotherexample, the catalytic resin mixture 106 is formed by blendinghomogeneous or heterogeneous catalytic particles into the pre-preg resinby a ratio of weights, such as the ratio of substantially 12% catalyticparticles by weight to the weight of resin. The ratio by weight ofcatalytic particles in the resin mixture may alternatively be in therange of 8-16% of catalytic particle weight to the total weight ofresin. It is understood that other blending ratios may also be used, andit may be preferable to use smaller particles. In one example of theinvention, the catalytic particle density is chosen to provide a meandistance between catalytic particles on the order of 3 u-5 u.

FIG. 1A dielectric 102 is faced with top foil 104A and bottom foil 104B.FIG. 1B shows a laser drilling process, whereby apertures 106 are formedby application of high power optical energy, such as from a laser whichelevates the temperature of the foil 104A and dielectric 102sufficiently to ablate (vaporize) the copper 102 and dielectric 104until the bottom surface 104B is reached. A typical aspect ratio (depthof via divided by diameter) for laser drilling which provides forsuccessful subsequent electroplating is in the approximate range 0.5 to1.0. The objective of laser drilling 106 in FIG. 1B is to provide smalldimension vias for subsequent use in interconnecting traces formed fromfirst foil 104B to second foil 104A. The thickness of the foil 104B isrelated to the trace width, the thicker the foil 104A, 104B, the widerthe resulting traces will be, and the wider the traces are, the thickerthe dry film which is used during a subsequent trace pattern step. Intension with the desire for thin copper foil 104B is the thermaldissipation requirement that bottom copper foil 104B have sufficientthickness to withstand laser drilling step 106. Accordingly, thethickness of first copper surface 104B is governed by the minimumthickness required to withstand the laser drilling of hole 106 withoutbreaking through the lower foil 104B, which also limits how narrow thelinewidth and spacing of the resultant trace can be.

The drilling of holes and vias for removal of surface copper andunderlying dielectric may be by laser ablation, where the temperature ofthe catalytic pre-preg is instantly elevated until the catalyticpre-preg is vaporized. It may be preferable to use a laser with awavelength with a low reflectivity and high absorption of this opticalwavelength for the pre-preg material being ablated, such as ultraviolet(UV) wavelengths. Examples of such UV lasers are the UV excimer laser oryttrium-aluminum-garnet (YAG) laser, which are also good choices becauseof the narrow beam diameter and high available power which for formingchannels of precise mechanical depth and with well-defined sidewalls.

For a non-catalytic laminate, the drilled vias may receive a catalyticsurface treatment known as “desmearing” to enable electroless plating. Atypical desmearing process of figure includes a permanganate treatmentto remove residues through vigorous oxidation, a neutralizer treatmentwhich neutralizes the permanganate, the application of a surfacecatalyzer such as palladium for enabling electroless copper plating,after which it is possible to perform an electroless plating stepwhereby the via and through hole surfaces are coated with copper forconnectivity of the top copper foil to bottom copper foil.Alternatively, catalytic particles may be added to the resin of thedielectric to form a catalytic dielectric, for which electroless platingmay be performed on drilled holes with only a cleaning operation.

FIG. 1C shows the completion of the subsequent electroless plating step.The electroless plating thickness 108 is the minimum required touniformly coat drilled via 106 and provide electrical connectivity tofoil layers 104A and 104B for a subsequent electroplate operation shownin FIG. 1E.

FIG. 1D shows a patterning step, whereby resist 110A is applied on topsurface 104A and a blanket resist is applied 110B to bottom surface104B. Resist (also known as photoresist for patterns formed by exposureto optical energy) or masks (mechanical barriers which forms the desiredpatterns) 110A and 110B of FIG. 1D or 210A and 210B of FIG. 2F may beliquid photoresist, dry film photoresist, metal masks, or other maskingmaterial which has a low etch rate compared to the etch rate of thesurrounding exposed copper. The photoresist thickness is typicallychosen based on copper/photoresist etch selectivity, such that removalof copper through etching leaves sufficient resist at the end of theetch. Typical dry film thickness is in the range of 0.8-2.5 mil (20-64u) and the dry film thickness is selected commensurate with the line(trace width)/space (gap between traces) resolution of the finishedtraces. For example, dry film thickness of 0.8 mil may be used for 1-1.5mil trace line/space requirements, 1.2 mil dry film may be used for1.1-2 mil trace line/space, and 1.5 mil dry film may be used for1.75-2.5 mil line/space requirements. When electroplating occurs asshown in step 1E, only the exposed copper regions receive copperdeposition 112, which forms what are known as “dot vias” (where tracesare subsequently formed).

FIG. 1F shows the result of a first smoothing step, whereby a partialremoval of excess copper and photoresist from an original layer 114 to anew planar level with dot vias 112-1 reduced in height along with resist110A-1. Surface smoothing may be accomplished many different ways, forexample using a 420 to 1200 grit abrasive applied on a planar surfacewith mild pressure and linear or rotational agitation between the boardand planar surface to provide a grinding operation. Other methods forplanarizing the surface may be used, including milling or machiningusing chemical processes, mechanical processes, or other methods forforming a planar surface. Bottom surface resist 110B is not smoothed, asthis process is intended for forming dot vias only.

FIG. 1G shows a resist strip step, where resist 110A-1 and 110B of FIG.1F is removed using a solvent or plasma asking process.

FIG. 1H shows a second smoothing step, whereby the pedestal dot viaregions 112-1 of FIG. 1G are planarized down to the foil surface 104A.The reason for performing intermediate planarization of step 1F is toavoid grinding metal and photoresist onto the foil surface 104A. Byperforming this planarization in a two-step process, the firstplanarization 1F provides a uniform surface and less material to removeduring the final planarization of FIG. 1H.

FIG. 1I shows the drilling of through holes 116, which is followed byelectroless plating in FIG. 1J which deposits copper on the innersurface of the hole 116, the application of pattern resist 118 to one orboth sides in step 1K, and electroplate in step 1L which forms traces onexposed copper surfaces (relying on the top and bottom blanket layer ofexposed electroplate copper which provides the single electrode) andinside surfaces of plated through holes 120. The exposed electroplatedcopper regions subsequently receives a thin layer of tin plate as etchresist over any exposed copper not covered by resist.

FIG. 1M shows the board after stripping the resist 118 which may also beused to form interconnecting traces (not shown) with the vias 120. Atthis point, the vias 120 have surface regions which are tin plated(thereby resisting ammonia based copper etchants such as ammoniumchloride or ammonium sulfate) and the comparatively thin exposed copperelectroless deposition (and underlying foil) on surfaces 104A and 104B,which are etched using a copper etchant such as an ammonia basedetchant, producing the result shown in FIG. 1N. The thin deposition oftin is also etched away using an etchant such as nitric acid, leavingcopper traces (not shown), though holes, and as vias shown in FIG. 1N.

FIGS. 2A through 2J show an alternative process for forming vias on theorder of 3.5 mil diameter (optionally in the range of 2-5 mil) andtraces on the order of 1 mil width and 1 mil spacing, which are greatlyimproved over the approximately 3 mil linewidth capability of the stepsshown in the series of FIG. 1A through 1N, and with a reduction in thenumber of required steps. FIG. 2A shows dielectric 202 which islaminated with a top thin foil 204A and a backing foil 203 whichprotects the thin foil 204A. Similarly, thin bottom foil 204B islaminated onto dielectric 202 along with removable backing foil 205which is in intimate contact with thin backing foil 204B. The thin topfoil 204A and thin bottom foil 204B are approximately 0.12 to 0.15 mil(3 u-4 u) thick and are layered with backing foil 203 and 205, eachbacking foil having a thickness of approximately 0.75 mil (18 u). Topbacking foil 203 may be removed from thin foil 204A at any time prior toelectroless plating of step 2E, although bottom backing foil 205 iscritical for the laser drilling step of FIG. 2C. FIG. 2B shows adetailed region 207 of FIG. 2A, showing dielectric 202, thin bottomcopper foil 204B, and comparatively thick backing foil 205. In oneexample of the invention, thin bottom foil 204B and backing foil 205 areprovided in sheet form, and are laminated under elevated temperaturesuch as 350 to 400° F. and pressure such as 200 to 250 PSI ontocatalytic laminate 202 along with top foil 204A to mechanically attachtop foil 204A and bottom foil 204B to catalytic dielectric 202. Thelamination step for bonding of foils 204A and 204B to the laminate 202does not alter the ease of removal of backing copper foil 205, whichacts as a heat sink for thin foil 204B during the laser drillingoperation of FIG. 2C.

FIG. 2C shows the result of drilling blind via 206 such as by laserablation, and through holes 216, such as by laser ablation ormechanical. As before, the aspect ratio of blind vias by a laserablation or drilling operation should be in the approximate range 0.5to 1. FIG. 2D shows the circuit board layer after removal of the lowerbacking foil 205 of FIG. 2C, such as by peeling backing foil 205 frombottom thin foil 204B. As in FIG. 1B, the laser ablation or drillingoperation may be followed by a “desmearing” operation for non-catalyticlaminate, or the laminate itself may be catalytic, as described earlier.Either method ensures that drilling of a blind hole or through holeusing a laser, mechanical means, or chemical means results in anaperture with exposed surface catalytic material which provideselectroless plating as shown in FIG. 2E.

FIG. 2E shows the cross section view after electroless copperdeposition, with electroless copper 217 deposited on surfaces of theblind via 206, thru hole 216, and copper foil 204A and 204B.

FIG. 2F shows a cross section view after application of patternedphotoresist 210A and 210B, where the areas without resist are areaswhere traces will form.

FIG. 2G shows a cross section view after a copper electro-plating step,which deposits copper on all exposed copper areas not concealed byresist, including the via, drill hole walls, and any other copper traceregions not covered by the patterned photoresist.

FIG. 2H is a tin plating step, whereby any exposed copper regionsreceive a thin tin plate which acts as an etch resist during asubsequent copper etching step.

FIG. 2I shows a cross section view after stripping the resist, and FIG.2J shows the completed circuit board layer after etching the exposedcopper (regions not coated with tin in the step of FIG. 2H), and etchingthe exposed tin, which leaves the dot vias 220, traces, and platedthrough holes 216.

The process which results in the two layer board of FIG. 2J may beexpanded to form multi-layer board, with a structure known as “stackedvias”, where the via for a single layer has an aspect ratio of 0.5 to0.1, while providing connectivity across as many layers as is needed,with the via of each successive layer axially concentric with the via ofeach preceding layer. FIGS. 3A through 3H describe the additionalprocessing steps for forming multi-layer circuit boards from a centralcore 304.

FIG. 3A shows a two layer core 304 corresponding to the core of FIG. 2J,with filled vias and traces present. New top layer 302 comprising adielectric 308 with a top foil 310 and new bottom layer 306 withdielectric 312 and bottom foil 314 are added. These may also includethin foils which have backing foil which has been removed. FIG. 3B showsthe new top layer 302 and new bottom layer 306 laser drilled vias 320,322, 324, 326, and FIG. 3C shows the inner surfaces 328 of the vias haveexposed catalytic particles, either by a desmearing operation (whichadds catalytic particles to the inside surfaces of the drilled vias) orhave catalytic particles in the new top layer 302 dielectric and newbottom layer dielectric 306 which are exposed by the drilling operationof step 3B.

FIG. 3D shows electroless plating deposition 330, and FIG. 3E shows theaddition of pattern resist 340 to the new top layer and new bottomlayer. FIG. 3F shows the result of electro-plating deposition 342 whichforms filled vias and traces, and FIG. 3G shows the resist 340 stripped.FIG. 3H shows the end result 4 layer board, where the stacked vias areinterconnected above and below each other, and the vias and traces areformed by layers 342, 330 and 310, which are separately shown in thedrawings but act as a single uniform electrical layer. The process stepsof FIG. 3A to 3H may be iteratively repeated to add two additionallayers on each iteration, with the resulting last step of FIG. 3Htreated as the new core for the next iteration of processing startingwith FIGS. 3A to 3H. The relative scale of traces to dielectricthickness are exaggerated for clarity in understanding the structures.

FIGS. 4A through 4J show cross section views of an inner core circuitlayer formed using the semi-additive process, where the top layer tracesare formed using a catalytic laminate substrate 402 having thecharacteristic of a resin-rich surface which excludes catalyticparticles unless a channel is formed into the surface of the catalyticlaminate. The catalytic particles are generally uniformly distributed inthe catalytic laminate below an exclusion depth below each surface. InFIG. 4A, the top surface of the catalytic laminate is bare, and thebottom surface of the catalytic laminate has a thin foil 404B and thickbacking 405 formed from copper, the thin foil 404B laminated to thecatalytic laminate 404B, with the thick backing foil 405 providing heatsinking capability, as previously described for FIG. 2 . Detail 407 ofFIG. 4B shows the catalytic laminate 402, thin foil 404B, and thickbacking foil 405, which have respective dimensions as was previouslydescribed for FIG. 2B. Step 4C shows laser drilled holes 406 and throughhole 416, where the drilled apertures expose catalytic particles in thecatalytic laminate 402, and channels 407 which will later form tracesare formed into the top surface, where the channels 407 are sufficientlydeep to expose underlying catalytic particles which are not present inthe native surface of the catalytic laminate until below the catalyticparticle exclusion depth. The via apertures 406 will later be filledwith copper using a “fast electroless copper” deposition process, suchas commercially available ethylenediaminetetraacetic acid (EDTA)process, or a process which utilizes Copper sulfate, formaldehyde, andsodium hydroxide, rather than the electroplate process described in FIG.2G. For this reason, the via apertures 406 are smaller, suchapproximately 2.5-3 mil diameter to permit the via to be filled usingthe fast electroless copper process. As was described in FIG. 2C, thebacking foil 405 acts as a heat sink during the via laser drilling toprevent the penetration of thin bottom foil 404B during laser drillingof vias 406. After the vias 406 are formed, the backing foil 405 isremoved, as shown in FIG. 4D.

FIG. 4E shows the result of a fast electroless copper bath such as theEDTA process, where the top surface channels 407, through hole 416 innersurfaces and inner volume, and thin copper foil 404B receive copperdeposition 417. The via apertures 406 are also filled during this step.

FIG. 4F shows the application of patterned bottom side resist 410 andblanket top side resist 411, which covers the areas where copper tracesand vias are desired. The exposed copper surfaces are subsequentlyetched in FIG. 4G, with the other areas protected by resist such as dryfilm 410 and 411. After a resist strip in step 4H, the two sided core iscomplete, with the foil conductors 404B and electroless plated areas 417and filled via 406 forming homogeneous copper traces and filled vias,thereby forming a finished core which may be further laminated as shownin FIGS. 5A through 5C, or FIGS. 3A to 3H.

FIG. 5A through 5C shows analogous multi-layer processing steps usingcatalytic laminate 508 and 510 as outer layers which are laminated tocore 504, which core may be formed using the process of FIG. 2A-2J, or4A-4J.

FIG. 5B shows the laminate of FIG. 5A with channels 512 formed on topand bottom surfaces of the catalytic laminate by removal of the surfacelayer in a region where a trace is desired. Optionally, an annular ringof material is removed around each via 520, 522, 524, and 526. Theremoval of surface material may be by laser ablation, where thetemperature of the catalytic pre-preg and 510 is instantly elevateduntil the catalytic pre-preg is vaporized, while leaving the surroundingpre-preg structurally unchanged, but exposing the underlying catalyticparticles. It may be preferable to use a laser with a wavelength havinga low reflectivity and high absorption of this optical wavelength forthe pre-preg material being ablated, such as ultraviolet (UV)wavelengths. Examples of such UV lasers are the UV excimer laser oryttrium-aluminum-garnet (YAG) laser, which are also good choices becauseof the narrow beam extent and high available power which for formingchannels of precise mechanical depth and with well-defined sidewalls. Anexample laser may remove material in a 0.9-1.1 mil (23 u to 28 u)diameter width with a depth governed by laser power and speed ofmovement across the surface. Another surface removal technique forforming channel 512 and associated annular ring is plasma etching, whichmay be done locally or by preparing the surface with a patterned maskwhich excludes the plasma from the surface layers 508 or 510, such as adry film photoresist or other mask material which has a low etch ratecompared to the etch rate of catalytic pre-preg. The photoresistthickness is typically chosen based on epoxy/photoresist etchselectivity (such that plasma etch to the desired depth of removal ofthe cured epoxy leaves sufficient photoresist at the end of the etch),or in the case of photoresist which is used as an electroplate mask, thethickness is chosen according to desired deposition thickness. Typicaldry film thickness is in the range of 0.8-2.5 mil (20-64 u). Plasmassuitable for etching the resin rich surface include mixtures of oxygen(O) and CF₄ plasmas, mixed with inert gasses such as nitrogen (N), orargon (Ar) may be added as carrier gasses for the reactive gases. A maskpattern may also be formed with a dry film mask, metal mask, or anyother type of mask having apertures. Where a mechanical mask is used,the etch resist may be applied using any of photolithography, screenprinting, stenciling, squeegee, or any method of application of etchresist. Another method for removal of the surface layer of pre-preg ismechanical grinding, such as a linear or rotational cutting tool. Inthis example, the pre-preg may be secured in a vacuum plate chuck, and arotating cutter (or fixed cutter with movable vacuum plate) may travel apattern defining the traces such as defined by x,y coordinate pairs of aGerber format photofile. In another example of removing surfacematerial, a water cutting tool may be used, where a water jet withabrasive particles entrained in the stream may impinge on the surface,thereby removing material below the surface to expose the underlyingcatalytic particles. Any of these methods may be used separately or incombination to remove surface material and form channel 512 intocatalytic dielectric 508 and 510, preferably with the channel extendingbelow the exclusion depth which exposes the catalytic particles belowthe surface. Accordingly, the minimum channel depth is the depthrequired to expose the underlying catalytic particles, which is acharacteristic of the cured catalytic pre-preg, such as one formedaccording to U.S. Pat. No. 9,706,650, also by the present inventors. Asthe catalytic material is dispersed uniformly through the cured pre-pregbelow the exclusion depth, the maximum channel depth is limited by thedepth of the woven fiber (such as fiberglass) fabric of the catalyticlaminate 508, 510, which tends to complicate channel cleaning, as thefibers may break off and re-deposit in channels intended for electrolessplating, or otherwise interfere with subsequent process steps. Typicalchannel depths are 1 mil (25 u) to 2 mil (70 u). The final step afterremoving the surface material to form the channel 510 is to clean awayany particles of material which were removed, which may be accomplishedusing ultrasound cleaning, jets of water mixed with surfactant, or anyother cleaning means which does not result in surface materialsurrounding the channel 512 from being removed.

Vias 520, 522, 524, 526 are next drilled such as by laser drilling,preferably for a small diameter such as 2.5 to 3 mil to allow a fastelectroless plating to fill the via apertures in a later step, andchannels 512 are formed such as by laser ablation, water cutting, plasmaetching, or any other form for removing the surface layer of thecatalytic laminate to below the exclusion depth. Electroless plating isperformed in step 5C, which deposits copper 530 on areas where surfacematerial has been removed from the catalytic laminate 508, 510, therebyforming conductive traces 530 in the channels 512, inner surfaces of via520, 522, 524, and 526, filling the via apertures to the outer surfaceof the added layers 502 and 506. The process steps of FIGS. 5A to 5C maybe iteratively repeated to add two additional layers on each iteration,with the resulting last step of FIG. 5C treated as the new core for thenext iteration of processing starting with FIGS. 5A to 5C.

The present invention may be practiced several different ways. It isunderstood that the core (central) circuit layer 304 of FIGS. 3A-3H or504 of FIGS. 5A-5C may result from either the catalytic or non-catalyticlaminate 202 of FIG. 2J or the catalytic laminate of FIG. 4J. Startingwith either core circuit layer of FIG. 2J or 4J, outer layers may beinterchangeably added using the electroless and electro-plating methodof FIGS. 3A to 3H, or the electroless plating method of FIGS. 5A to 5C.

In the present specification, “mil” is understood to be 0.001 inch,“approximately” is understood to mean less than a factor of 4 greater orsmaller, “substantially” is understood to mean less than a factor of 2greater or smaller. “Order of magnitude” of a value includes the rangefrom 0.1 time the values to 10 times the value. A “mil” is understood tobe 0.001 inch.

Certain post-processing operations are not shown which are generic toprinted circuit board manufacturing, and may be performed using priorart methods on boards produced according to the novel process. Suchoperations include tin plating for improved solder flow, gold flash forimproved conductivity and reduced corrosion, soldermask operations,silkscreening information on the board (part number, referencedesignators, etc.), scoring the finished board or providing breakawaytabs, etc.

1-14. (canceled)
 15. A process for forming a multi-layer circuit board having an inner core and one or more pairs of outer layers, the process comprising: forming said inner core on a catalytic dielectric, the catalytic dielectric having catalytic particles which are exposed when the catalytic dielectric is drilled, the catalytic dielectric having a thin top foil applied to the top surface of the dielectric and a thin bottom foil applied to a bottom surface opposite the top surface, the thin bottom foil overlaid with a removable backing foil which is thicker than the thin bottom foil; laser drilling at least one via through the thin top foil and the catalytic dielectric to the thin bottom foil without penetrating the thin bottom foil, removing the removable backing foil, and optionally drilling at least one through hole extending through the top foil, the catalytic dielectric and the thin bottom foil, said laser drilled at least one via and optional thru holes thereby exposing catalytic particles on drilled surfaces of the catalytic dielectric; electroless plating the exposed catalytic particles, said thin top copper foil, and said thin bottom copper foil; applying patterned resist to create exposed copper areas and concealed copper areas of the thin top copper foil and thin bottom copper foil; electroplating said exposed copper areas; tin plating said exposed copper areas; stripping said patterned resist; quick etching the inner core until the previously concealed copper areas are etched free of copper; thereby forming the inner core having a top surface and a bottom surface; said outer layer pairs formed by applying a dielectric layer to the top surface and a dielectric layer to the bottom surface of the inner core, each dielectric layer also having a thin outer surface foil, for each applied dielectric layer: laser drilling at least one via and one or more optional thru holes through the top surface dielectric layer or bottom surface dielectric layer to an underlying copper layer; the laser drilled holes having exposed catalytic particles; electroless plating the exposed thin copper foil and exposed catalytic particles; applying patterned resist to at least one said thin outer surface foil; electroplating the exposed surfaces; plating tin onto the electroplated areas; stripping the patterned resist; quick etching the exposed copper.
 16. The process of claim 15 where at least one of said thin outer surface foil layers is approximately 0.12 to 0.15 mil thick.
 17. The process of claim 15 where at least one of said outer layer vias is stacked over a corresponding inner layer via.
 18. The process of claim 15 where said quick etch is performed with an ammonia based etchant.
 19. The process of claim 18 where said ammonia based etchant includes at least one of ammonium chloride or ammonium sulfate. 20-21. (canceled)
 22. The process of claim 15 where the catalytic particles comprise at least one of: Palladium (Pd), platinum (Pt), rhodium (Rh), iridium (Ir), nickel (Ni), gold (Au), silver (Ag), cobalt (Co), copper (Cu), iron (Fe), manganese (Mn), chromium (Cr), molybdenum (Mo), tungsten (W), titanium (Ti), tin (Sn), or a palladium salt, including at least one of: BrPd, CL₂Pd, Pd(CN)₂, I₂Pd, Pd(NO₂)₂*2H₂O, Pd(NO₂)₂, PdSO₄, Pd(NH₂)4Br₂, or Pd(NH₂)4Cl₂H₂O.
 23. The process of claim 15 where the catalytic particles comprise an inorganic particle overlaid with a catalyst.
 24. The process of claim 23 where the catalyst is at least one of: Palladium (Pd), platinum (Pt), rhodium (Rh), iridium (Ir), nickel (Ni), gold (Au), silver (Ag), cobalt (Co), copper (Cu), iron (Fe), manganese (Mn), chromium (Cr), molybdenum (Mo), tungsten (W), titanium (Ti), tin (Sn), or a palladium salt, including at least one of: BrPd, CL₂Pd, Pd(CN)₂, I₂Pd, Pd(NO₂)₂*2H₂O, Pd(NO₂)₂, PdSO₄, Pd(NH₂)4Br₂, or Pd(NH₂)4Cl₂H₂O.
 25. A process for forming a multi-layer circuit board having an inner core and one or more pairs of outer layers, the process comprising: forming said inner core on an inner core catalytic dielectric, the inner core catalytic dielectric containing catalytic particles which are exposed when the catalytic dielectric is drilled, the catalytic dielectric also having a thin top foil applied to a top surface of the inner core dielectric and a thin bottom foil applied to a bottom surface opposite the inner core dielectric top surface, the thin bottom foil overlaid with a removable backing foil which is thicker than the thin bottom foil: laser drilling at least one via through the thin top foil, the dielectric, the at least one via reaching the thin bottom foil without penetrating the thin bottom foil; removing the removable backing foil; optionally drilling at least one through hole extending through the top foil, the dielectric and the thin bottom foil; said laser drilled via and optional drilled thru hole having inner surfaces with exposed catalytic particles from drilling; electroless plating the exposed catalytic particles, said thin top copper foil, and said thin bottom copper foil; applying patterned resist to create exposed copper areas and concealed copper areas of the thin top copper foil and thin bottom copper foil; electroplating said exposed copper areas; tin plating said exposed copper areas; stripping said patterned resist; quick etching the inner core until the previously concealed copper areas are etched free of copper; thereby forming the inner core having a top surface and a bottom surface; said outer layer pairs formed by applying a dielectric layer to the top surface and the bottom surface of the inner core, each dielectric layer also having a thin outer surface foil, and for each outer layer pair: laser drilling at least one via and one or more optional thru holes through the outer layer pair dielectric layer to an underlying copper layer; the laser drilled holes having exposed catalytic particles; electroless plating the exposed thin copper foil and exposed catalytic particles; applying patterned resist to at least one surface; electroplating the exposed surfaces; plating tin onto the electroplated areas; stripping the patterned resist; quick etching the exposed copper.
 26. The process of claim 25 where at least one of said foil layers is approximately 0.12 to 0.15 mil thick.
 27. The process of claim 25 where at least one of said outer layer vias is stacked over a corresponding inner layer via.
 28. The process of claim 25 where said quick etch is performed with an ammonia based etchant.
 29. The process of claim 29 where said ammonia based etchant includes at least one of ammonium chloride or ammonium sulfate.
 30. The process of claim 25 where the catalytic particles comprise at least one of Palladium (Pd), platinum (Pt), rhodium (Rh), iridium (Ir), nickel (Ni), gold (Au), silver (Ag), cobalt (Co), copper (Cu), iron (Fe), manganese (Mn), chromium (Cr), molybdenum (Mo), tungsten (W), titanium (Ti), tin (Sn), or a palladium salt, including at least one of: BrPd, CL₂Pd, Pd(CN)₂, I₂Pd, Pd(NO₃)₂*2H₂O, Pd(NO₃)₂, PdSO₄, Pd(NH₃)4Br₂, or Pd(NH₃)4Cl₂H₂O.
 31. The process of claim 25 where the catalytic particles comprise inorganic particles overlaid with a catalyst.
 32. The process of claim 31 where the catalyst is at least one of Palladium (Pd), platinum (Pt), rhodium (Rh), iridium (Ir), nickel (Ni), gold (Au), silver (Ag), cobalt (Co), copper (Cu), iron (Fe), manganese (Mn), chromium (Cr), molybdenum (Mo), tungsten (W), titanium (Ti), tin (Sn), or a palladium salt, including BrPd, CL₂Pd, Pd(CN)₂, I₂Pd, Pd(NO₃)₂*2H₂O, Pd(NO₃)₂, PdSO₄, Pd(NH₃)4Br₂, or Pd(NH₃)4Cl₂H₂O. 